Eduardo P. Mateus

Electrokinetic remediation of six emerging organic contaminants from soil

Some organic contaminants can accumulate in organisms and cause irreversible damages in biological systems through direct or indirect toxic effects. In this study the feasibility of the electrokinetic (EK) process for the remediation of 17β-oestradiol (E2), 17α-ethinyloestradiol (EE2), bisphenol A (BPA), nonylphenol (NP), octylphenol (OP) and triclosan (TCS) in soils was studied in a stationary laboratory cell. The experiments were conducted using a silty loam soil (S2) at 0, 10 and 20mA and a sandy soil (S3) at 0 and 10 mA. A pH control in the anolyte reservoir (pH>13) at 10 mA was carried out using S2, too. Photo and electrodegradation experiments were also fulfilled. Results showed that EK is a viable method for the remediation of these contaminants, both through mobilization by electroosmotic flow (EOF) and electrodegradation. As EOF is very sensible to soil pH, the control in the anolyte increased EOF rate, consequently enhancing contaminants mobilization towards the cathode end. The extent of the mobilization towards the electrode end was mainly dependent on compounds solubility and octanol-water partition coefficient. In the last 24h of experiments, BPA presented the highest mobilization rate (ca. 4 μg min(-1)) with NP not being detected in the catholyte. At the end of all experiments the percentage of contaminants that remained in the soil ranged between 17 and 50 for S2, and between 27 and 48 for S3, with no statistical differences between treatments. The mass balance performed showed that the amount of contaminant not detected in the cell is similar to the quantity that potentially may suffer photo and electrodegradation.

Characterization of the volatile fraction emitted by Pinus spp. by one- and two-dimensional chromatographic techniques with mass spectrometric detection

The chemical composition of the needles of P. pinea, P. pinaster, P. halepensis, P. nigra, P. brutia, P. patula, P. radiata, P. taeda, P. elliotti, P. kesiya, P. sylvestris and P. eldarica was investigated. Headspace solid-phase microextraction and steam distillation extraction were used to collect the volatile fractions. Samples were analyzed using one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GCxGC) associated with a quadrupole and a time-of-flight mass detectors. Results showed that the analytical capabilities of 1D-GC are partially limited by the separation power of the columns. The higher sensibility and the absence of peak skewing of the time-of-flight mass analyzer, with the use of automated peak finding and deconvolution algorithms, allowed for the detection of trace components with qualitative full spectra and the extraction of true mass spectra from coeluting compounds, promoting their reliable identification and thus significantly improving results obtained by 1D-GC/MS, when using a quadrupole mass analyzer. The use of GC x GC resulted in enhanced separation efficiency and increased signal to noise ratio (sensitivity) of the analytes, maximizing mass spectra quality and improving compound detection and identification. This work shows the use of 1D-GC/ToFMS for the analysis of pine needles volatiles, achieving the detection of 177 compounds, that is more than twice the number previously identified by standard 1D-GC/MS. The analysis by GC x GC for the same sample allowed the detection of 212 compounds. The enantioselective GC x GC analysis performed for all the Pinus spp. under study achieved the detection of 422 different compounds. Cross-over phenomena according to operational conditions are highlighted and discussed.

Pine volatiles mediate host selection for oviposition by Thaumetopoea pityocampa (Lep., Notodontidae)

The oviposition behaviour and host selection by females of the pine processionary moth, Thaumetopoea pityocampa, was studied under two conditions: in a field insectary and in a pine stand. An oviposition choice test was conducted in an insectary cage, using artificial Christmas trees (ACTs) baited with extracts from four pine species: Pinus pinea, Pinus pinaster, Pinus halepensis and Pinus brutia, plus a control. Females oviposited significantly more egg batches on the ACT baited with a P. brutia extract, while no oviposition occurred on the control ACT. In a large P. pinea stand, two groups of randomly selected trees were marked and baited respectively with an extract of P. brutia, which was the preferred species under insectary conditions and with a solvent, to act as control. Results showed that oviposition in the field followed an aggregated pattern, fitting a negative binomial distribution and that trees baited with P. brutia extracts, received a significantly larger number of egg‐batches than control trees. In parallel, the volatiles emitted by all pine extracts tested where analysed by gas chromatography and mass spectrometry (GC‐MS), coupled to a time‐of‐flight (TOF) mass analyser after solid phase microextraction (SPME), resulting in the identification of 26 compounds. Comparative chromatograms showed qualitative differences among the pine species used, some compounds being present in one of them only. Findings demonstrate for the first time that: (i) T. pityocampa females discriminate among bouquets extracted from different host pine species and exhibit oviposition preferences; and (ii) olfactory cues play an important role in mediating the selection process.

Regressional modeling of electrodialytic removal of Cu, Cr and as from CCA treated timber waste : application to sawdust

Waste of wood treated with chromated copper arsenate (CCA) is expected to increase in volume over the next decades. Alternative disposal options to landfilling are becoming more attractive to study, especially those that promote re-use. The authors have studied and modeled the electrodialytic (ED) removal of Cu, Cr and As from CCA treated timber waste. The method uses a low-level direct current as the “cleaning agent”, combining the electrokinetic movement of ions in the matrix with the principle of electrodialysis. The technique was tested in eight experiments using a laboratory cell on sawdust of out-of-service CCA treated Pinus pinaster Ait. poles. The experiments differ because the sawdust was saturated with different assisting agents and different percentages of them. In order to select the best assisting agent in jointly removing the three metals and subsequently the best percentage of the selected assistant agent, a statistical analysis was made. First, three experiments were selected as being the best. Second, for the selected experiments, a polynomial model was found to describe the time evolution of the total concentrations of each metal in the electrolytes. Based on this modeling, a multi-treatment regression approach was further used to select the final range of experiments.

Differentiation of ten pine species from central portugal by monoterpene enantiomer-selective composition analysis using multidimensional gas chromatography

SummaryThe composition of the volatile terpenes emitted by different trees has been successfully used as markers in a wide variety of studies such as chemotaxonomy. In this work discrimination among ten pine species,P. pinea, P. pinaster, P.brutia, P. elliotti, P.halepensis, P. kesiya, P. radiata, P. patula, P. sylvestris, andP. taeda was achieved by analyzing the relative composition of their volatile emissions. The analysis was performed after simultaneous distillation extraction; 16 monoterpenes were identified. My means of principal component analysis it was shown that discrimination among species could be maximized by taking into account three monoterpenes only-α-pinene, β-pinene, and limonene. In a second stage of the work the extracts were submitted to enantiomer-selective multidimensional gas chromatography (MDGC). The enantiomer ratio was determined after separation on a tailor-made 2,3-dimethyl-6-O-tert-butyldimethylsilyl-β-cyclodextrin analytical column. Application of principal component, analysis to the samples enabled their comparative characterization.

Climate Warming and Past and Present Distribution of the Processionary Moths (Thaumetopoea spp.) in Europe, Asia Minor and North Africa

Pine processionary moth, Thaumetopea pityocampa, is a model insect indicator of global warming, the northwards and upwards range expansion of this Mediterranean species being directly associated with the recent warming up. The knowledge about the drivers of moth expansion is synthesized. A first standardized mapping of the northern expansion edge, from Western Europe to Turkey, is presented, then detailed for 20 countries of Europe, Asia Minor and North Africa, including future trends. Additional data about the responses of the other Thaumetopoea species are given. Finally, the chapter points out the importance of the man-mediated introductions in the expansion process.

Assessment of combined electro-nanoremediation of molinate contaminated soil

Molinate is a pesticide widely used, both in space and time, for weed control in rice paddies. Due to its water solubility and affinity to organic matter, it is a contaminant of concern in ground and surface waters, soils and sediments. Previous works have showed that molinate can be removed from soils through electrokinetic (EK) remediation. In this work, molinate degradation by zero valent iron nanoparticles (nZVI) was tested in soils for the first time. Soil is a highly complex matrix, and pollutant partitioning between soil and water and its degradation rates in different matrices is quite challenging. A system combining nZVI and EK was also set up in order to study the nanoparticles and molinate transport, as well as molinate degradation. Results showed that molinate could be degraded by nZVI in soils, even though the process is more time demanding and degradation percentages are lower than in an aqueous solution. This shows the importance of testing contaminant degradation, not only in aqueous solutions, but also in the soil-sorbed fraction. It was also found that soil type was the most significant factor influencing iron and molinate transport. The main advantage of the simultaneous use of both methods is the molinate degradation instead of its accumulation in the catholyte.

Genetic Diversity and Structure at Different Spatial Scales in the Processionary Moths

This chapter presents the evolutionary history of Thaumetopoea species associated with pines, at different temporal and spatial scales. It corresponds to recent discoveries and ongoing works using sequencing technologies and population genetics. Most of the subchapters focus on the winter pine processionary moths T. pityocampa/T. wilkinsoni including a population with a shifted life cycle. Results concerning the summer pine processionary moth T. pinivora and the evolution of the whole genus are also presented. This chapter gives insights about the effects of Quaternary climate changes in different regions, and allow to study the contemporary changes due to the present climate warming.

Water stress affects Tomicus destruens host pine preference and performance during the shoot feeding phase

Abstract• The effect of water stress on host selection and performance during the shoot feeding phase, by the Mediterranean pine shoot beetle Tomicus destruens, was studied.• Young potted Pinus pinaster plants were subjected to two water supply regimes: (i) well watered; (ii) 4–5 months of moderate drought stress. Plant volatile organic compound (VOCs) emissions were collected by SPME and analysed by GC/MS.• In tests with paired plants, the number of holes and tunnels excavated by beetles in well watered pines was significantly larger than in stressed plants, whereas in no-choice tests no differences occurred.• Beetle survival was significantly higher on well watered, than on stressed pines (p = 0.006), while fat contents also increased (p = 0.09).• Plants could be assigned to treatments based on VOCs emissions, stressed pines emitting more myrcene and less β-pinene than well watered ones.• It is concluded that during the shoot feeding phase, T. destruens preferentially attacks non-stressed plants, in detriment of stressed ones, upon which a higher fitness is attained.• The role of pines VOCs emissions under moderate drought stress, in the host selection and colonization process by the pine shoot beetle, is discussed.

Electrically induced displacement transport of immiscible oil in saline sediments.

Electrically assisted mitigation of coastal sediment oil pollution was simulated in floor-scale laboratory experiments using light crude oil and saline water at approximately 1/10 oil/water (O/W) mass ratio in pore fluid. The mass transport of the immiscible liquid phases was induced under constant direct current density of 2A/m(2), without water flooding. The transient pore water pressures (PWP) and the voltage differences (V) at and in between consecutive ports lined along the test specimen cell were measured over 90days. The oil phase transport occurred towards the anode half of the test specimen where the O/W volume ratio increased by 50% over its initial value within that half-length of the specimen. In contrast, the O/W ratio decreased within the cathode side half of the specimen. During this time, the PWP decreased systematically at the anode side with oil bank accumulation. PWP increased at the cathode side of the specimen, signaling increased concentration of water there as it replaced oil in the pore space. Electrically induced transport of the non-polar, non-conductive oil was accomplished in the opposing direction of flow by displacement in absence of viscous coupling of oil-water phases.